ALBERT

Description: We present the 2320-2050 cm-1 (4.31-4.88 micrometers) infrared spectra of 16 solid-state nitriles, isonitriles, and related compounds in order to facilitate the assignment of absorption features in a spectral region now becoming accessible to astronomers for the first time through the Infrared Space Observatory (ISO). This frequency range spans the positions of the strong C triple bond N stretching vibration of these compounds and is inaccessible from the ground due to absorption by CO2 in the terrestrial atmosphere. Band positions, profiles, and intrinsic strengths (A values) were measured for compounds frozen in Ar and H2O matrices at 12 K. The molecular species examined included acetonitrile, benzonitrile (phenylcyanide), 9-anthracenecarbonitrile, dimethylcyanamide, isopropylnitrile (isobutyronitrile), methylacrylonitrile, crotononitrile, acrylonitrile (vinyl cyanide), 3-aminocrotononitrile, pyruvonitrile, dicyandiamide, cyanamide, n-butylisocyanide, methylisocyanoacetate, diisopropylcarbodiimide, and hydrogen cyanide. The C triple bond N stretching bands of the majority of nitriles fall in the 2300-2200 cm-1 (4.35-4.55 micrometers) range and have similar positions in both Ar and H2O matrices, although the bands are generally considerably broader in the H2O matrices. In contrast, the isonitriles and a few exceptional nitriles and related species produce bands at lower frequencies spanning the 2200-2080 cm-1 (4.55-4.81 micrometers) range. These features also have similar positions in both Ar and H2O matrices, and the bands are broader in the H2O matrices. Three of the compounds (pyruvonitrile, dicyandiamide, and cyanamide) show unusually large shifts of their C triple bond N stretching frequencies when changing from Ar to H2O matrices. We attribute these shifts to the formation of H2O:nitrile complexes with these compounds. The implications of these results for the identification of the 2165 cm-1 (4.62 micrometers) "XCN" interstellar feature and the 4550 cm-1 (2.2 micrometers) feature of various objects in the solar system are discussed.

Description: The infrared spectra of CO frozen in nonpolar ices containing N2, CO2, O2, and H2O and the UV photochemistry of these interstellar/precometary ice analogs are reported. The spectra are used to test the hypothesis that the narrow 2140 cm-1 (4.673 microns) interstellar absorption feature attributed to solid CO might be produced by CO frozen in ices containing nonpolar species such as N2 and O2. It is shown that mixed molecular ices containing CO, N2, O2, and CO2 provide a good match to the interstellar band at all temperatures between 12 and 30 K both before and after photolysis. The optical constants (real and imaginary parts of the index of refraction) in the region of the solid CO feature are reported for several of these ices. The N2 and O2 absorptions at 2328 cm-1 (4.296 microns) and 1549 cm-1 (6.456 microns), respectively, are also shown. The best matches between the narrow interstellar band and the feature in the laboratory spectra of nonpolar ices are for samples which contain comparable amounts of N2, O2, CO2, and CO. Co-adding the CO band from an N2:O2:CO2:CO = 1:5:1/2:1 ice with that of an H2O:CO = 20:1 ice provides an excellent fit across the entire interstellar CO feature. The four-component, nonpolar ice accounts for the narrow 2140 cm-1 portion of the feature which is associated with quiescent regions of dense molecular clouds. Using this mixture, and applying the most recent cosmic abundance values, we derive that between 15% and 70% of the available interstellar N is in the form of frozen N2 along several lines of sight toward background stars. This is reduced to a range of 1%-30% for embedded objects with lines of sight more dominated by warmer grains. The cosmic abundance of O tied up in frozen O2 lies in the 10%-45% range toward background sources, and it is between 1% and 20% toward embedded objects. The amount of oxygen tied up in CO and CO2 frozen in nonpolar ices can be as much as 2%-10% toward background sources and on the order of 0.2%-5% for embedded objects. Similarly 3%-13% of the carbon is tied up in CO and CO2 frozen in nonpolar ices toward field stars, and 0.2%-6% toward embedded objects. These numbers imply that most of the N is in N2, and a significant fraction of the available O is in O2 in the most quiescent regions of dense clouds. Ultraviolet photolysis of these ices produces a variety of photoproducts including CO2, N2O, O3, CO3, HCO, H2CO, and possibly NO and NO2. XCN is not produced in these experiments, placing important constraints on the origin of the enigmatic interstellar XCN feature. N2O and CO3 have not been previously considered as interstellar ice components.